CN105712899B - A kind of method of Supported Co compound for catalysis alkohol and amine one-step synthesis imines - Google Patents
A kind of method of Supported Co compound for catalysis alkohol and amine one-step synthesis imines Download PDFInfo
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- CN105712899B CN105712899B CN201410740926.4A CN201410740926A CN105712899B CN 105712899 B CN105712899 B CN 105712899B CN 201410740926 A CN201410740926 A CN 201410740926A CN 105712899 B CN105712899 B CN 105712899B
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Abstract
The invention belongs to technical field of chemistry and chemical engineering, specially a kind of method of Supported Co compound for catalysis alkohol and amine one-step synthesis imines.To load cobalt compound as catalyst, in the case where having solvent or solvent-free state, air or oxygen is oxygen source, is reacted 1~48 hour at 30~120 DEG C, you can by the corresponding group with imine moiety of alkohol and amine one-step synthesis.Described load cobalt compound is, using vitamin B12 as presoma, to be obtained after inert atmosphere is calcined.The catalyst of the present invention is cheap, be easy to get, and can be recycled, and activity and selectivity performance is excellent.
Description
Technical field
It is specially with Supported Co compound for catalysis alkohol and amine one-step synthesis imines the invention belongs to technical field of chemistry and chemical engineering
Method.
Background technology
Imines is the important organic intermediate and part of a class, and also has very heavy in medical particularly anticancer, anti-inflammatory agent
Apply.Traditional imines is synthesized by prepared by aldehyde and primary amine dehydrating condensation, but because aldehydes has peculiar smell and unstable, because
This has developed many other methods for preparing imines.For example pass through the oxidative coupling or the dehydrogenation oxidation of secondary amine of primary amine, although
Good effect is obtained preparing symmetrical group with imine moiety, but shows not good enough for asymmetric imines, it usually needs choosing
The larger primary amine of the active difference of two classes is selected, and could obtain preferable yield, bottom under a kind of amount of substrate excess conditions wherein
Thing scope is also narrow.More and more people are caused by the imines of oxidative coupling one-step synthesis various structures using alkohol and amine recently
Concern, this method, as substrate, using air or oxygen as oxidant, reacts unique by-product only using the alcohol relatively stablized, easily obtained
There is water generation, therefore react more convenient, green.
The heterogeneous catalyst of the existing imine compound by alkohol and amine one-step synthesis is concentrated mainly on Au, Pt, Pd etc.
Noble metal catalyst.Because its is expensive and resource scarcity, and large-scale synthesizing imine compound is not applied to.Although
There is the report of non-precious metal catalyst, but generally require to add the catalyst of stoichiometry, and in the bar of excessive alcohol or amine
The result of satisfaction could be obtained under part.And for homogeneous catalysis system, because it can not avoid shortcoming, such as：Catalyst is difficult to follow
Ring, the shortcomings of product separation is difficult.Therefore, explore a kind of easy preparation and cheap multiphase non-precious metal catalyst is in gentle bar
Alkohol and amine synthesizing imine class compound is a very meaningful and full of challenges job by an efficient step under part.
The content of the invention
In order to solve above-mentioned the deficiencies in the prior art, the present invention is using non-precious metal catalyst is loaded, in a mild condition,
To realize alkohol and amine one-step synthesis group with imine moiety：
Using supported cobalt compound as catalyst, alkali is added or is added without as auxiliary agent, molecular oxygen or air are oxygen source, 30
Under the conditions of~120 DEG C, 1~48h of stirring reaction, by alkohol and amine one-step synthesis imine compound, reaction expression is as follows：
Wherein,
R1For aryl, heteroaryl, the C of substituted base on 2-, 3-, or 4- position2-C8Alkyl, C2-C8Alkylene, C2-C8Alkynes
Base,
Aryl be phenyl, naphthyl, anthryl, phenanthryl, heteroaryl be furyl, thienyl, pyridine radicals,
Substituent is phenyl, halogen, nitro, C1-C4Alkoxy, C1-C8It is more than one or both of alkyl or hydrogen；
R2For aryl, the heteroaryl of substituted base on 2-, 3-, or 4- position, C4-C8Straight chained alkyl or C5-C6Cycloalkyl,
Substituent is phenyl, halogen, nitro, C1-C4Alkoxy, C1-C8It is more than one or both of alkyl or hydrogen；
R1And R2It is identical or different；
Using the organic macrocycle compound containing cobalt as cobalt precursor, in N2Or under Ar atmosphere, when being calcined for 200~1000 DEG C
Between 0.5-5h, you can obtain supported cobalt compound catalyst.
The preferable temperature for being calcined cobalt precursor is 600~800 DEG C.
Organic macrocycle compound containing cobalt is one kind in vitamin B12, Cobalt Phthalocyanine, Cobalt Porphyrin or salen Co.
Course of reaction uses balloon oxygen supply, or uses bubbling or autoclave pressure pressurising oxygen supply.
The mass ratio of catalyst and alcohol is 0.05~0.5:1.
The mass ratio of auxiliary agent and alcohol is 0~1:1, auxiliary agent is carbonate, bicarbonate, phosphate, sodium hydroxide, hydroxide
The one or more of potassium or ethylate.
The mol ratio of alcohol and amine is 0.5~2：1.
Organic solvent is added in reaction system, organic solvent is toluene, ethylbenzene, dimethylbenzene, C5~C10One in alkane
Plant or two or more.
Beneficial effects of the present invention
The catalyst of the present invention is cheap, be easy to get, and can be recycled, and activity and selectivity performance is excellent.
Embodiment
Implementation below helps to understand the present invention, but is not restricted to present invention.
Embodiment 1
Using vitamin V B12 as presoma, it is catalyzed needed for being obtained after 800 DEG C of nitrogen atmosphere roasting 2h, natural cooling room temperature
Agent.0.5mmol phenmethylol and 0.5mmol aniline, 10mg catalyst, using 1mL heptane to be molten are added in Schlenk bottles
Agent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding imines, and chromatogram yield is 97%.
Embodiment 2
Catalyst preparation as described in Example 1, in Schlenk bottles add 0.5mmol phenmethylol and 0.5mmol to first
Base aniline, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding
Imines, separation yield is 96%.
Embodiment 3
Catalyst preparation as described in Example 1, in Schlenk bottles add 0.5mmol phenmethylol and 0.5mmol to chlorine
Aniline, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding
Imines, separation yield is 97%.
Embodiment 4
Catalyst preparation as described in Example 1, adds 0.5mmol phenmethylol and 0.5mmol hexamethylene in Schlenk bottles
Amine, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding Asia
Amine, separation yield is 99%.
Embodiment 5
Catalyst preparation as described in Example 1, in Schlenk bottles add 0.5mmol phenmethylol and 0.5mmol just oneself
Amine, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding Asia
Amine, separation yield is 98%.
Embodiment 6
Catalyst preparation as described in Example 1, in Schlenk bottles add 0.5mmol to methylbenzyl alcohol and 0.5mmol
Aniline, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding
Imines, separation yield is 97%.
Embodiment 7
Catalyst preparation as described in Example 1, added in Schlenk bottles 0.5mmol to chlorobenzene methanol and 0.5mmol
Aniline, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding
Imines, separation yield is 96%.
Embodiment 7
Catalyst preparation as described in Example 1, adds 0.5mmol cinnamyl alcohol and 0.5mmol benzene in Schlenk bottles
Amine, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding Asia
Amine, separation yield is 88%.
Embodiment 8
Catalyst preparation as described in Example 1, adds 0.5mmol n-heptanol and 0.5mmol benzene in Schlenk bottles
Amine, 10mg catalyst, using 1mL heptane as solvent, air balls are oxygen source, the stirring reaction 12h at 100 DEG C, obtain corresponding Asia
Amine, separation yield is 10%.
Claims (5)
1. a kind of method that supported cobalt compound Co-C-N is catalyzed alkohol and amine one-step synthesis imines, it is characterised in that to load
Type cobalt compound Co-C-N is catalyst, adds or be added without alkali as auxiliary agent, molecular oxygen or air are oxygen source, 30~120 DEG C
Under the conditions of, 1~48h of stirring reaction, by alkohol and amine one-step synthesis imine compound, reaction expression is as follows：
Wherein,
R1For aryl, heteroaryl, the C of substituted base on 2-, 3-, or 4- position2-C8Alkyl, C2-C8Alkylene, C2-C8Alkynyl,
Aryl be phenyl, naphthyl, anthryl, phenanthryl, heteroaryl be furyl, thienyl, pyridine radicals,
Substituent is phenyl, halogen, nitro, C1-C4Alkoxy, C1-C8It is more than one or both of alkyl or hydrogen；
R2For aryl, the heteroaryl of substituted base on 2-, 3-, or 4- position, C4-C8Straight chained alkyl or C5-C6Cycloalkyl,
Substituent is phenyl, halogen, nitro, C1-C4Alkoxy, C1-C8It is more than one or both of alkyl or hydrogen；
R1And R2It is identical or different；
Using the organic macrocycle compound containing cobalt as cobalt precursor, in N2Or under Ar atmosphere, in 200~1000 DEG C of roasting times
0.5-5h, you can obtain supported cobalt compound catalyst Co-C-N；
Organic macrocycle compound containing cobalt is one kind in vitamin B12, Cobalt Phthalocyanine, Cobalt Porphyrin or salen Co；
Organic solvent is added in reaction system, organic solvent is toluene, ethylbenzene, dimethylbenzene, C5~C10One kind in alkane or
It is two or more.
2. according to the method described in claim 1, it is characterised in that the preferable temperature of roasting cobalt precursor is 600~800 DEG C.
3. according to the method described in claim 1, it is characterised in that the mass ratio of catalyst Co-C-N and alcohol is 0.05~0.5:
1。
4. according to the method described in claim 1, it is characterised in that the mass ratio of auxiliary agent and alcohol is 0~1:1, auxiliary agent is carbonic acid
It is more than one or both of salt, bicarbonate, phosphate, sodium hydroxide, potassium hydroxide or ethylate.
5. according to the method described in claim 1, it is characterised in that the mol ratio of alcohol and amine is 0.5~2：1.
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| CN108144612B (en) * | 2016-12-02 | 2020-12-29 | 中国科学院大连化学物理研究所 | Cobalt-based catalyst for synthesizing carboxylic ester by one-pot method and preparation and application thereof |
| CN107216269B (en) * | 2017-05-18 | 2019-06-04 | 山西师范大学 | Hydroxylating phenanthroline copper complex/O2The method of catalysis oxidation alkohol and amine cross-coupling synthesizing imine |
| CN109232308B (en) * | 2018-09-26 | 2022-11-29 | 河南师范大学 | Method for preparing imine by catalyzing amine and alcohol cross coupling by using copper catalyst |
| CN111269141B (en) * | 2020-03-10 | 2023-02-17 | 广东石油化工学院 | Method for synthesizing imine by catalyzing alcohol-amine with NNN cobalt complex |
| CN115646501B (en) * | 2022-10-28 | 2023-07-14 | 东北石油大学 | Cobalt monoatomic catalyst synthesized by molten salt method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5091545A (en) * | 1990-03-02 | 1992-02-25 | The Goodyear Tire & Rubber Company | Catalytic oxidation of hydroxy containing aromatic compounds |
| WO2004060833A2 (en) * | 2002-12-31 | 2004-07-22 | Rhodia Chimie | Process for synthesizing amine from nitrile |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5091545A (en) * | 1990-03-02 | 1992-02-25 | The Goodyear Tire & Rubber Company | Catalytic oxidation of hydroxy containing aromatic compounds |
| WO2004060833A2 (en) * | 2002-12-31 | 2004-07-22 | Rhodia Chimie | Process for synthesizing amine from nitrile |
Non-Patent Citations (2)
| Title |
|---|
| Cobalt Nanoparticles on Charcoal ： A Versatile Catalyst in the Pauson−Khand Reaction, Hydrogenation, and the Reductive Pauson−Khand Reaction;Seung Uk Son et al.;《ORGANIC LETTERS》;20021010;第4卷(第22期);第3983-3986页 * |
| 后修饰法合成介孔钴金属有机框架及其催化烯烃环氧化;沙莎 等;《应用化学》;20140731;第31卷(第7期);第799-805页 * |
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